The simultaneous synthesis of 5-hydroxymethyl-2-furoic acid and 2,5-hydroxymethylfuran from biomass-derived 5-hydroxymethyl furan was developed using a solvent-free mechanochemical approach.
This Review summarizes recent efforts to capitalize on 5hydroxymethylfurfural (HMF) and related furans as emerging building blocks for the synthesis of fine chemicals and materials, with a focus on advanced applications within medicinal and polymer chemistry, as well as nanomaterials. As with all chemical industries, these fields have historically relied heavily on petroleum-derived starting materials, an unsustainable and polluting feedstock. Encouragingly, the emergent chemical versatility of biomass-derived furans has been shown to facilitate derivatization towards valuable targets. Continued work on the synthetic manipulation of HMF, and related derivatives, for access to a wide range of target compounds and materials is crucial for further development. Increasingly, biomass-derived furans are being utilized for a wide range of chemical applications, the continuation of which is paramount to accelerate the paradigm shift towards a sustainable chemical industry.
Herein, we report
a modular synthetic route to access tetra-arylated
thiophene compounds with four different substituents with programmed
chemical control provided by an ester activating/directing group.
This method enables the functionalization of individual positions
of thiophene sequentially via regioselective halogenations and cross-coupling
reactions. The reaction sequence described provides tetra-arylated
thiophenes in higher yields than previous routes and employs practical
reaction protocols, simple catalytic systems, and short reaction times.
Oligothiophenes are important organic molecules in a number of burgeoning industries as semi‐conducting materials due to their extensive π‐conjugation and charge transport properties. Typically, non‐symmetric, di‐aryl‐substituted thiophenes are prepared by the successive formation of Grignards, organotin, and/or boronic acid intermediates that can be subsequently employed in cross‐coupling reactions. While reliable, these approaches present synthetic difficulties due to the reactivity of organo‐metallic/pseudo‐metallic species, and produce considerable amounts of waste due to necessary pre‐functionalization. We have developed a decarboxylative cross‐coupling route as an effective strategy for the modular and less wasteful synthesis of a wide range of non‐symmetric, di‐arylthiophenes. This method uses a thiophene ester building block for successive decarboxylative palladium‐catalyzed couplings that allows for the efficient synthesis and evaluation of the opto‐electronic properties of a library of candidate semi‐conductors with functional groups that could be challenging to access using previous routes.
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